NAS-NS-3002[Rev.) RA OF ARSENIC Rev.1965 NUCLEARSCIENCESERIES National Academy of Sciences-National Research Council Pubtished by: United States Atomic Ener~ Commission COMMM’EE ON NUCLEhR SCIEWE S. K AllL90n, Chairman R D. EVWIS,Vice Chairman University of Chicago Mass. Institute o! Technology L9wIESlack, Secretary Natlomd Ffeeearch @UIICfl E. C. Andereon Bernd Kahn I.OeAlamos *1. Uibcm3tory Taft Sanitary EI@neertng Center N. E. -U Jerry B. *ion U.S. Naval Badtological Defense IAxmatory Untversiw of Muylend M$uttn J. Berger R L. PlatEman Nattoual Bureau of ~ Argome National Laboratory C. J. Borkowakf Erneet C. Polfard CkikRtdge NatL Laboratory Peoneylvauia State Univerei~ Robert G. Cocbmn Kathertne Way A & M Coflege of Tame M Rtdge National IAoratory Herbert Goldetetn George W. Wethertll Columbte htvem3itY University of California (Los Angeles) Paul c. Aeb9reold Ralph G. Allen Atomtc Energy Commiaeioo w Force Office of Scientific Reeeweh J. Howard Mcbfillen Nationn.1Sctence Foundation smmmllmm~ N. E. -U, Chairman W. E. Nervlk U. & Navel F?adiol.agtcalIMfenee Lawrence Radiation Latmratory laborato~ J, M. Niefe.en G. R ChoPPtn General Hlectic Company (HicW) Florida State Unlvereity G. D. O’KeUey H. X Clark M Rtdge Nattonel IAoratory FtenmeelaerPolytechnic Inetttute R P. Scbuman R IL DtelllODd Atomtc Energy Dlvlsion I.awrence Hadiatloo Laboratory Phillipe Petroleum Company (Idaho Falls) A W. Fsdrhell E. P. Steinberg Urdversity of Weehlngton Argonne Wtlonel IAmratory Jerome Hudte D. N. Hundermen Brooffhaven National Mratory HattelLeMemorlnl IneUtute J. D. lh@t J. W. Whmhester be Almnoe &temUflc Klxuatory -eachusetts Inetitute of Technology RADIOCHEMISTRY OF ARSENIC HAROLDC. BEARD Florida State University, Tallahassee, Florida, January 1960 revised by J. G. CUNINGHAME Atomic Energy Res earth Establi shrnent, Harwell, Didcot, Berkshire, England, January 1965 Iszmed: November 1965 Subcommittee on Radiochemistry National Academy of Sciences—National Research Council Printed in USA. Price $1.00. Available from the Clearinghouse for Federal Scientific and Technical Information, National Bureau of Stim3ards, U. S. Department of Commerce, Springfield, Virginia. 22151 FOREWORD The Subcommittee on Radiochemidry IB one of a nmtir of subcommittees working under the Ccsmnlttee on IVuclear Science within the National Academy of Sc~enceO - Nat Ional Research council. Its mmkrs repreeent government, industrial, end university laboratories i.n the areL3B of radiochemistry and nuclear chemistry. Support for the actltitles of this end other subcomlttees of the Comittee on Ituclear Science 1S provided by a Brent from the Rational Science Foundation. The subcommittee has concerned itself with preparation of publications, encowaglng and supporting activities in nuclear education, sponsoring symposia on selectad current topics In mdiochemistry and nuclear chemistry, and investigating Bpecid problems as they arise. A Eeriea of monographs on the mdio- chemistry of essentially all the e~nts and ou rsdiochemlcal techniques is k-sing published. Initiation and enco~nt of publlcat Ion of articles on nuclear education in various subject areas of chemistry have occurred, and development and m~ nt of cerkain education activitieO (e. g., laboratory and demonstration experltnents with ~dioactivlty) have &en encouraged and amlsted. Radioactive contendnatlon of reagentB end materials has been investigated and specific recwmendations made. This series of monographs has resulted from the need for comprehensive compilations of radiochemlcal and nuclear chemical information. Each mono~ph collectO in one vohme the perttient information required for mdioclwmical wurk with an individual element or with a specialized technique. The U. S. Atcmic Energy Coxmlssion IME sponso~d the printing of the series. Comnents and suggestions for further publications and activi- ties of value to persons worldng with mdioactivityare welccmed by the Subconmitt&e. N. E. hlk)ll, Chainuen Subcommittee on Rediochemiatry iii Preface to the revised edition A considerable number of papers have appeared in the literature on the radiochemismy and chernis try of arsenic since the first edition of the monograph was published. The general form and much of the original content of the monograph has been retained, subs tantial additions being made where necessary. The reviser would like to thank Mr. R. W. Clarke, Information Officer of the Chemistry Division, A. E. R. E., for his great help in conducting a very thorough literature search. iv I A selection of general reviews of the inorganic and analytical chemistry of arsenic. 1 n General reviews of the radiochemistry of arsenic. 2 III Summary of statistical physical properties of arsenic. 2 IV Table of isotopes. 3 v Decay schemes. 6 VI y-spectra. 13 VII Relevant portion of chart of the nuclides. 17 Review of the chemistry of arsenic of interest b radiochemists. 19 IX Dissolution of arsenic samples. 23 x Counting techniques pertinent to arsenic isotopes. 23 xl General remarks concerning the detailed radiochemical procedures of Section XII. 24 XII Collection of detailed radiochemical procedures. 25 v RADIOCHEMISTRY OF ARSENIC HAROLD C. BEARD Florida State University, Tallahassee, Florida, January 1960 revised by J. G. CUNINGHAME Atomic Energy Research Establishment Harwell, Didcoq Berkshire, England, January 1965 I. A SELECTION OF GENERAL REVIEWS OF THE INORGANIC AND ANALYTICAL CHEMISTRY OF ARSENIC Mellor, J. W., “A Comprehensive Treatise on Inorganic and Theoretical Chemistry,” Volume 9, Chapter 51, pp. 1-338, Longmans, Green and Co., Inc., New York, 1947. Sidgwick, N, V., “The Chemical Elements and Their Compounds,” Volume 1, pp. 758-803, Oxford University Press, London, 1950. Sneed, M, C. and Brasted, R, C., “Comprehensive Inorganic Chemis~,” Volume 5, Introduction pp. 3-10, Chapter 2, pp. 106-152, D. Van Nostrand Co., Princeton, N.J,, 1956. Remy, H. “Treatise on In organic Chemistry” Elsevier Amsterdam, 1956. Jacobsen, C. A., “Encyclopedia of Chemical Reactions,” pp. 264-500, Reinhold Publishing Co., 1946. McAlpine, R. K., and Soule, B. A., “Qualitative Chemical Analysis,” 4th Edition D. Van Nostrand Co., Inc., New York, 1956. Holness, H., “Advanced Inorganic Qualitative Analysis, ” pp. 75-79 and pp. 152-153, Pitman and Sons, I--6ndon, 1957, Willard, H. H. and Diehl, H., ‘Advanced Quantitative Analysis, ” pp. 339-345, D. Van Nostrand Co., New York, 1943. Walton, H. F., “Principles and Methods of Chemical Analysis, ” pp. 161-163 and pp. 411-412, Prentice-Hall, Inc., New York, 1952, Hillebrand, W. F., Lundell, G. E. F., BrighL H. A. and Hoffman, J. I., “Applied Inorganic Analysis, ” Chapter 13, pp. 256-272, 2nd Edition, John Wiley and Sons, New York, 1953. Chariot, G. and Bejier, D. translated by Murray, R. C., “Quantitative Inorganic Analysis, ” pp. 335-342, Methuen and Co., London; John Wiley and Sons, Inc., New York, 1957. Furman, N. H., ‘Standard Methods of Chemical Analysis” 6th Edition. Vol. 1 pp. 106-107, Van Nostrand, New York, 1962. II. GENERAL REVIEWS OF THE RADIOCHEMISTRY OF ARSENIC Smales, A. A., “Neutron Activation Analysis,” Chapter 19, pp. 518-545 in Yoe, J. H. and Koch, J. J., Jr., “Trace Analysis,” John Wiley and Sons, New York, 1957. m. SUWARY OF STATISTICAL PHYSICAL PROPERTIES OF ARSENIC(l) Outer electronic configuration 4s2 4p3 Molecular state of gas As4# AS2 Atomic volume, 13.13 ml. (metal) Melting poin~ 814.5°C. (36 atm). Boiling point, sublimes at 610°C, Density, 5.7 g/cc (meh~); 3,9 g/cc (yellow) :%: :Vv:t!:l:kA&12:22 ~ ; AS+3 0.69~ ; AS+5 (As033 0.47 ~ Ionization potential,m 10 e,v, Electxonegativity, 2.0 on the Pauling scale. Principal oxidation states, -3, +3, +5 EO, As + 3 H20 < H3As03 + 3 H+ + 3 e-, -0.25 V. (H.As02); AS02 + 21-120 s H3As04 + 2 H+ + 2 e-, -0.559 v. Heat capacity, 0.082 cal/gram. IV TABLE OF ISOTOPES Some methods of Prtyfl:nltpos Energy of principnl lher~ of principal I130tope Half life preparation &radiations MeV c:;:ELw”.f total ~s where shown) h“ 7m ae7’3(p,3n) @ As” 15m Ge’lp, 21J E.C. (W%) /9+ (--97%) 2.9 AE70 57xn C+e70(d, h) E.C. (3%) d. S,70 (3+ (lo%) 1.44 E.C. (5.3%) p (74.7%) 2.144 E.C, (0.1 S%) @ (’.1%) 2.89 Y 1.04 Aa71 ‘~ 0e70(d,n) /3+ (3%) 0.25 d. Se71 /? (’%) 0.79 E.C. (58%) @ (33%) 0.813 0.175 Y E.C. (21.2%) @ (3.6%) ~ (56.2%) 2.50 @ (19%) 3.34 0.630 (8) Y 0,835 (75) Y A873 76d t3e72(d, n) E. C. d. Se73 Y o,o135(e/y > 1300) o,054(0/y - 5) [N.B. These ~a W. from decay of Ge73m, ~ 0.333]. ~a71b ~ AS74 I’. sd E.C. (< 1%) ~e74(d’ ~ )S+ (< 0.1%) Ge74(p, n) E.C. (38%) A8WJ> k) P (25%) 0.92 E.C. (2.2%) f? (2.8%) 1.53 IT (16%) 0.69 ~ (16%) 1.36 Y 0996 (80) Y 0,635(20) As’s 100% natural abundnrme An76 2d.5h An’s(n, @ ~ (5,1%) As’s (d, p) ~ (6.9%) 1.748 ~79 ~ ~ /T (35%) 2.405 S076 (n: p) F (53%) 2.965 Y 0.559 (71) Y 0.65S (6) Y 1.127 (16) ~e76 (d ~ Aa77 39h F (2,5%) fis.sim p (97.5%) 0.69 d. (3677 y (weak) 0.0S6 (4) y (Weakil 0.160 (7) y (wenkl 0.246 (67) y (weak) 0.524 (22) 3 some methods of Principal types Energy of principal Energy of princlpnl Half life Iaotapo preparation of decay /kndiationa MeV lj:~:~;l$o shown) ~slh ~ 91m ~ (30%) 1.4 se”+% p) E (70%) 4.1 fianicm d. 0.270 Ge7’ Y 0.610 Y 0.800 Y 1.2-90 Y 2,680 Y 9m Smy, p) /T (5%) ,@bl,pn) E (95%) 2.15 Seg2(d, an) #&o 15.35 SWII, p) & (0.8%) P- (4.3%) 3,7 F (3.5%) 4.1 B- (1.7%) 4.2 6- (1.4%) 4,5 ~- (32%) 5.4 & (56%) 6.0 0.66 Y 31s Stwy, p) 19- (100%) 3.s 4 For further information on the radiations of the arsenic isotopes see:- B.